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Open Archive Toulouse Archive Ouverte (OATAO)
OATAO is an open access repository that collects the work of Toulouse researchers and
makes it freely available over the web where possible.
This is an author-deposited version published in: http://oatao.univ-toulouse.fr/
Eprints ID: 4500
To cite this version:
Gerbaud, Vincent and Gabas, Nadine and Blouin, jacques and Crachereau,
Jean-Christophe (2010) Study of wine tartaric salt stabilization by addition of
carboxymethylcellulose (CMC). Comparison with the « protective colloïds »
effect. Journal international des sciences de la vigne et du vin, vol. 44 (n° 3).
pp. 135-150. ISSN 1151-0285
Any correspondence concerning this service should be sent to the repository
administrator: staff-oatao@inp-toulouse.fr1 Study of wine tartaric acid salt stabilization by
2 addition of carboxymethylcellulose (CMC): comparison
3 with the « protective colloïds » effect
4
5 GERBAUD Vincent (1,2), GABAS Nadine (1,2), BLOUIN Jacques (3) and
6 CRACHEREAU Jean Christophe (4).
7
(1)
8 Université de Toulouse, INP-ENSIACET, UPS, LGC (Laboratoire de
9 Génie Chimique), 4 allée Emile Monso - BP 84234 - 31030 Toulouse cedex 4,
10 France
(2)
11 CNRS, LGC (Laboratoire de Génie Chimique), 4 allée Emile Monso - BP
12 84234 - 31030 Toulouse cedex 4, France
(3)
13 Robin-2, 33141 Villegouge, France
(4)
14 Chambre d’Agriculture de la Gironde, Service Vin, 39 rue Michel
15 Montaigne, F-33290 Blanquefort, France
1617 Abstract
18 Aims: Inhibition of potassium hydrogen tartrate (KHT) crystallization by
19 carboxymethylcellulose (CMC) is tested in a model solution and in wines. Tartaric
20 acid salt crystallization risk is assessed by computing the supersaturation, saturation
21 temperature and excess KHT with respect to the saturation equilibrium using
22 MEXTAR® ("Mesure de l’EXces de TARtre") software.
23 Materials and results: Firstly, the time for crystals to appear was recorded by
24 monitoring the conductivity in a model solution and in a wine, and the inhibition ratio
25 was computed. At 11.5°C, 0.5 mg.L-1 CMC inhibited KHT crystallization. The
26 inhibitory effect increased exponentially with increasing CMC concentration and was
27 several times greater than that of polysaccharides and polyphenols, the protective
28 colloids in wine (Gerbaud et al., 1997). At 2°C, 30 mg.L-1 CMC had the same
29 inhibitory effect than 10 mg.L-1 at 11.5°C.Secondly, 20 red and white wines were
30 refrigerated for 3 weeks at -4°C with CMC or metatartaric acid. Results show that the
31 addition of 20 mg.L-1 CMC has an inhibitory effect at least equivalent to 100 mg.L-1
32 metatartaric acid. Furthermore, for 10 wines preheated for 8 days at 30°C and then
33 refrigerated for 2 months at 0°C, 5 and 20 mg.L-1 CMC maintains its inhibitory
34 efficiency, unlike metatartaric acid which is hydrolysed
35 Significance and impact of the study: The OIV-OENO 366-2009 and OIV-OENO
36 02/2008 resolutions recently authorized the use of CMC to prevent tartaric acid salt
37 precipitation. With no impact on health, and stable under heating and in acid solution,
38 CMC is an efficient candidate for tartaric stabilization. The optimal concentration of
39 20 mg.L-1 (2 g.hL-1) should however be adapted to local wine storage conditions and
40 KHT crystallization risk.
41 Key words: CMC, tartaric acid salts, crystallization, precipitation, additives
4243 Résumé 44 L’effet de la carboxymethylcellulose (CMC) sur la cristallisation du bitartrate de 45 potassium KHT est évalué dans une solution modèle et dans des vins. Le risque de 46 cristallisation est mesuré par calcul de la sursaturation, de la température de saturation 47 et du KHT en excès par rapport à l’équilibre de saturation avec le logiciel 48 MEXTAR® (Mesure de l’EXces de TARtre). 49 Premièrement, le temps pour voir apparaître des cristaux est enregistré par suivi de 50 la conductivité dans une solution modèle et dans un vin et le rapport d’inhibition est 51 calculé. A 11,5°C, 0,5mg.L-1 de CMC inhibe la cristallisation du KHT. L’effet 52 inhibiteur croit exponentiellement avec la concentration et est plusieurs fois supérieur 53 à celui des colloïdes protecteurs du vin, polysaccharides et polyphénols (Gerbaud et 54 al., 1997). A 2°C, 30mg.L-1 de CMC est aussi efficace que 10mg.L-1 à 11,5°C. 55 Puis, on démontre que 20mg.L-1 of CMC est un inhibiteur equivalent à 100mg.L-1 56 d’acide métatartrique dans 20 vins rouges et blancs, réfrigérés pendant 3 semaines à - 57 4°C. Enfin, dans 10 vins préchauffés 8 jours à 30°C puis réfrigérés 2 mois à 0°C, 58 l’acide métatartrique s’hydrolyse et perd son efficacité mais pas 5 et 20mg.L-1 de 59 CMC . 60 En accord avec les résolutions OIV-OENO 366-2009 et OIV-OENO 02/2008 61 autorisant la CMC pour prévenir les précipitations tartriques, ces résultats démontre 62 l’efficacité de cet additif sans effet sur la santé, stable à la chaleur et dans les 63 conditions d’acidité des vins. La concentration efficace de 20mg.L-1 (2g.hL-1) devra 64 cependant être validée avec les conditions locales de conservation des vins et de leur 65 risque de cristallisation. 66 67 Mots clés: CMC, sels tartriques, cristallisation, précipitation, additif
1. Tartaric stabilization overview
Potassium hydrogen tartrate (KHT) and calcium tartrate (CaT) crystallization is governed by the
solid Ŕ liquid equilibrium of potassium and calcium ions with L(+)-tartaric acid. Consumers usually
dont appreciate the presence of crystals in a wine bottle that can also cause excessive gushing (and
loss of product) in sparkling wines. The crystallization of tartaric acid salts (tartrates) naturally occurs
during alcoholic fermentation and continues during wine storage, either voluntarily by physical
treatment or involuntarily after alkaline salt deacidification. Removing both cations and anions from
the wine affects the pH, total acidity and buffering power of the wine (Devatine et al., 2002;
Blouin and Peynaud, 2005).
According to the crystallization theory, tartaric acid salts “crystallize” rather than “precipitate”,
because the rates of crystal nucleation and growth remain moderate with respect to truly precipitating
salts for which very high local supersaturation makes crystal appearance almost immediate (Ratsimba,
1990; Gerbaud, 1996).
Compared to the solubility product of KHT and CaT, the elevated concentration in potassium and
calcium, the main wine cations, and tartaric acid, the main wine anion (Blouin and Cruege, 2003;
Taillandier and Bonnet, 2005) causes a supersaturation in both salts, and therefore a potential risk of
crystallization in wine (Gerbaud, 1996). The saturation level of KHT and CaT decreases in time under
cold storage conditions. The higher the supersaturation, the faster the crystallization rates, which is
why mini-contact or freezing tartaric stabilization is recommended before winter (Blouin and
Peynaud, 2005). Supersaturation is defined as a ratio of the salt ion composition in wine versus the
salt ions compositions under saturation conditions. It can be computed by solving the thermodynamic
equations describing the solid Ŕ liquid and dissociation equilibrium dependent on pH, taking into
account the activity coefficients from the ionic strength, either approximately (Berg and Keefer, 1958;
Usseglio-Tomasset et al., 1992) or rigorously, accounting also for the tartaric acid salt complexes
(Scollary, 1990; Cardwell et al., 1991; Gerbaud, 1996). Rigorous KHT and CaT supersaturation
calculations are routinely done with the help of software like MEXTAR (Blouin et al., 1998).
Alternatively, a wine is supersaturated if its temperature is below its saturation temperature, which
can be computed (Blouin et al., 1998) or measured by monitoring the conductivity directly (Würdig et
al., 1982; Maujean et al., 1985, Garcia-Ruiz et al., 1991) or indirectly with the Stabisat® apparatus
(Ratsimba and Gaillard, 1988; Gaillard et al., 1990; Favarel, 1991; Tusseau and Feneuil, 1992).
There are basically three methods for preventing tartaric acid salt crystallization in bottled wines:
1. processes that induce salt precipitation before bottling by means of cooling the wine:
stabulation process (Berg and Keefer, 1958; Brugirard and Rochard, 1991), "contact"
process (Carles, 1892; Rhein, 1977; Müller-Spath, 1977, Rhein and Neradt, 1979; Blouin
et al., 1979) and various continuous processes (Ratsimba, 1990);
42. processes that selectively remove excess potassium and/or calcium ions: ion exchange
resin process (Clutton, 1974) or electrodialysis (Moutounet et al., 1991; Moutounet et al.,
1994);
3. processes that use crystallization inhibitors, such as metatartaric acid (Peynaud and
Guimberteau, 1961), yeast mannoproteins (Lubbers et al., 1993; Moine and Dubourdieu,
1995; Moine-Ledoux et al., 1997; Moine-Ledoux and Dubourdieu, 2002) and at last
carboxymethylcellulose gums (CMC) that we are concerned with in this study
(Wucherpfennig et al., 1984; Crachereau et al., 2001; Tusseau, 2009; Motta et al., 2009).
As pointed out at a recent technical workshop on wine tartaric stabilization (Favarel, 2009), all
processes are worth investigating when facing a risk of tartaric acid salt crystallization, even those
having drawbacks. For example, cooling processes are expensive to set up and operate and may be
partly inefficient if the wine supersaturation is too low or in red wine where natural colloids inhibit
crystal nucleation and growth. Electrodialysis is relatively cheap to operate but requires expensive
equipment and may induce pH increase that is sometimes not wanted. Metatartaric acid is extremely
efficient until it hydrolyses naturally after a few months or after a few days under heating, releasing
then tartaric acid that reinforces supersaturation. Yeast mannoproteins are efficient inhibitors at a
concentration of 200 mg.L-1 in some wines. But for highly saturated wines where a higher
concentration is needed to achieve the same inhibitory effect, mannoprotein flocculation may occur
that counteracts the expected effect.
CMC effect in model solutions and in wines was studied in laboratory conditions from 1993 to
1998 as part of a PhD project (Gerbaud, 1996) and in subsequent years at the Gironde Chamber of
Agriculture (CA33) in Blanquefort, in collaboration with the "Laboratoire de Génie Chimique" UMR
CNRS 5503 in Toulouse. Having obtained a 3-year experimentation agreement under the article 26 of
the EEC n°822/27 regulation, the CA33 studied the effect of CMC on large volumes of wine from
various French wine production areas. The results of this 3-year study were presented at the XXVth
World Congress of Vine and Wine in Paris, June 2000 and published by Crachereau et al. (2001).
Crachereau et al. noted that CMC has a remarkable effect on preventing tartaric precipitation. The
laboratory results obtained between 1993 and 1998 were not published in the scientific literature. The
present article aims at publishing these data, in the context of the recent "Office International des
Vins" resolutions, OIV-OENO 366-2009 (monography on carboxymethylcelluloses (cellulose gums))
and OIV-OENO 02/2008 (Wine Ŕ Treatment using cellulose gum (Carboxymethylcellulose)) that
specifies the use of CMC for wine tartaric stabilization. In 2001, a preliminary study on CMC by the
CA33 was transmitted to the OIV and recalled when these resolutions were issued.
After a short introduction on the methods and tools that allow quantification of the inhibitory
effect of an additive versus tartaric acid salt precipitation, the study conditions, the wines and the
solutions are presented. The efficiency of CMC is assessed in model solution by recording the
induction time and is studied in wine by observing the presence or absence of crystals after several
5weeks of cold storage at -4°C. Furthermore, CMC is compared to metatartaric acid, in particular to
evaluate its ability to withstand heat while maintaining its protective effect.
2. Quantifying the effect of « protective colloïds » and other
additives on tartaric precipitations
Tartaric stabilization processes using additives mimic the « protective colloïds » effect. Indeed,
wines, red ones in particular, have been suspected for many years to prevent or slow tartaric salt
crystal appearance (nucleation) and to lower the efficiency of cold tartaric stabilization (Carles, 1892;
Berg, 1953; Balakian and Berg, 1968; Brugirard, 1979). Later, the inhibitory effect of wine colloids
was confirmed (Wücherpfennig et al., 1984; Maujean et al., 1985; Maujean et al., 1986; Rodriguez-
Clemente and Correa-Gorospe, 1988; Lubbers et al., 1993; Moine and Dubourdieu, 1995; Gerbaud et
al., 1997; Dubourdieu and Moine, 1997; Moine-Ledoux et al., 1997; Moine-Ledoux et Dubourdieu,
2002) and the polysaccharides and polyphenols involved were identified (Gerbaud et al., 1997;
Vernhet et al., 1999a; Vernhet et al., 1999b; Doco et al., 2000).
The effect of an additive on crystallization depends on its concentration at a given temperature
(Mullin, 1993). Among the additives cited above, only metatartaric acid is considered as a complete
inhibitor of tartaric salt crystal nucleation and growth, until its hydrolysis occurs. Other additives
merely slow crystal appearance and possibly their growth.
2.1. Evaluating the crystallization risk by computing the
supersaturation
Supersaturation (S) is the ratio of the wine state versus the saturation state, which is expressed by
the thermodynamic solubility product. For KHT, S equals:
2
mK mHT , KHT
S (1)
*
K solu bility
where
KHT: mean activity coefficient of potassium hydrogen tartrate, which varies with ionic
strength and temperature,
mi: molality of free (not involved in complexes) ion i (in mol.kg-1),
K*solubility: thermodynamic solubility product that, according to solid Ŕ liquid equilibrium
thermodynamics varies only with temperature, pressure and alcohol content (% v/v) for a
given reference state (taken here as atmostpheric pressure).
By definition, the saturation temperature of a wine is the temperature at which S = 1.
The distribution of ions in solution, mi, is computed by solving the solid Ŕ liquid and the
dissociation equilibrium together with the electroneutrality equation. It should also consider the
complexation equilibrium of approximately 12% of potassium and 10% of tartaric acid in wines
6(Gerbaud, 1996) and that concerning calcium (Scollary, 1990; Cardwell et al., 1991). Complexes
sequester free ions that could participate in crystallization. Mi depends on the pH and the ion
distribution through the ionic strength I. As pointed out by Berg and Keefer (1958) and Usseglio-
Tomasset (1995), the mean ionic strength I in wine is 0.04 mol/kg, making wine a diluted solution like
any other electrolyte solution for which simple Debye-Hückel equation can be used to compute
activity coefficients (Zemaitis et al., 1986). Solving the Debye-Hückel equation with I = 0.04 mol/kg
gives ± KHT = 0.83 at 25°C. MEXTAR® solves all the rigorous equilibrium equations for
hydroalcoholic solutions and wines between 8 and 16% v/v and provides an accurate value for the pH
and the saturation temperature of tartaric acid salts (Blouin et al., 1998; Devatine et al., 2002;
Gerbaud et al., 2003). Neglecting the complexes and the impact of ionic strength on the activity
coefficients leads to an overestimatation of supersaturation by 10% and an underestimation of pH by
0.1 to 0.2 pH units between pH 3 and 4 (Gerbaud, 1996).
At ambient temperature before the stabilization treatment, most of the wines are supersaturated:
their saturation temperature is higher than the ambient temperature and they may crystallize (Gerbaud,
1996). When temperature decreases or when the percentage of alcohol (v/v) increases, tartaric acid
salt solubility decreases and thus supersaturation increases along with the risk of tartaric precipitation.
2.2. Effect of additives on crystal appearance
By monitoring the conductivity under constant temperature, the induction time, that is the time
needed for crystals to appear, can be recorded. The inhibition ratio (IR) is defined as the ratio of the
induction time with and without additive in the same solution and at the same temperature (Gerbaud,
1996). This is the best experimental protocol to compare additives because it records primary
nucleation, which is the main phenomenon responsible for crystal appearance in bottled wines under
normal storage conditions.
Other indirect measurements of the additive effect have been used: the mini-contact test records
secondary nucleation induced at the surface of crystals added to the wine. Secondary nucleation is
faster than primary nucleation and may occur on particles in the wine or imperfections (scratches and
residues) on the bottle. Coupled with conductivity monitoring, the mini-contact test was used to prove
the inhibitory effect of CMC (Tusseau, 2009; Motta et al., 2009). Monitoring the conductivity drop
during crystal growth enabled Maujean et al. (1986) to assess the effect of inhibitors on growth and
they found that metatartaric acid completely blocked crystal growth. The refrigeration test detects the
presence or absence of crystals in wine after keeping it under high supersaturation conditions, for
instance 3 weeks at -4°C. But it enables, at best, to assess how inefficient is an additive.
2.3. Review of tartaric acid salt precipitation inhibition by
« protective colloids”
Gerbaud et al. (1997) studied the effect of wine polysaccharides, in particular type I and II
rhamnogalacturonans (RG-I and RG-II) and arabinogalactan-protein (AGP0, AGP2, AGP3, AGP4),
wine mannoproteins (MP0-a, MP0-b, MP0-c, MP0 total, MP1, MP2), wine polyphenols, and
7mannoproteins extracted from yeast cells (MPlev et MPlev-a), by recording the induction time in a
model solution (12% v/v alcohol, 2.42 g.L-1 KHT, 2 g.L-1 K2SO4, pH=3.77, Tsat=27°C) equivalent to
1.93 g.L-1 of tartaric acid and 1.39 g.L-1 of potassium. The crystallization risk was evaluated by
computing its supersaturation, namely S=1.67 at T=11.5°C, and by measuring a mean induction time
without additive equal to tind 1hr 20 min 15 min (Gerbaud, 1996).
Under S=1.67 at T=11.5°C, polyphenols are the best inhibitor, with an inhibition ratio of IR=5 at a
concentration of 2000 mg.L-1 and IR=180 at 4000 mg.L-1. However, such polyphenol concentration
cannot be added to a wine without signficant modification of its organoleptic features. RG-II favors
crystal nucleation up to 100 mg.L-1 but inhibits it above that concentration with IR~1.2 to 1.4. RG-I,
AGP0, AGP2, AGP3 and AGP4 are also weak inhibitors of crystal nucleation with R~2 to 3 at 20 mg.L-
1
. Regarding mannoproteins, the fractions MP0-a, MP0-b, MP0-c, MP0 total, MP1 and MP2 found in
wine are slightly inhibitory with IR~2 at 20 mg.L-1. Yeast cell mannoproteins MPlev and MPlev-a are
much better inhibitors with IR>150 at 150 mg.L-1. When temperature is lowered to 2°C (S=2.38), the
inhibitory effect of MPlev and MPlev-a is lowered as IR=30 at 530 mg.L-1.
According to Gerbaud et al. (1997), those « protective colloids » effects are coherent with the
commonly acknowledged behavior of white and red wines. White wines have low polyphenol content
and are rich in RG-II, with concentrations between 20 and 50 mg.L-1 that correspond to concentrations
where RG-II is a promoter of crystal nucleation. Red wines contain all the studied colloids, in
particular polyphenols in concentrations between 1000 and 4000 mg.L-1 and RG-II in concentrations
above 100 mg.L-1, within the range where an inhibitory effect is observed on tartaric acid salt
precipitation.
3. Use of CMC in wine
3.1. Features of the commercial CMCs used in this study
The commercial CMCs used in this study are the same as those used by Crachereau et al. (2001).
They match the features authorized by the O.I.V. in the OIV-OENO 366-2009 regulation, which
describes the CMC to be used in wine for tartaric stabilization. CMC are polymers of cellulose rings
substituted by carboxymethyl organic acid chemical groups often saturated by sodium. Pure CMC
pKa is around 4.3 and under wine pH conditions, about 20% of the carboxymethyl groups carry
negative charges in solution.
CMC BLANOSE 7LF (Aqualon Ŕ France) has a low substitution degree (SD=0.65 to 0.90)
and a low polymerization degree, which leads to a moderate viscosity between 25 and 50
mPa for a 2% solution at 25°C. Of food quality grade, its purity is greater than 99.5%
(incl. less than 0.4% of sodium glycolate). Its pH for a 2% solution is close to 7.
CMC WALOCEL CRT 10 G (Wolff Walsrode Ŕ Germany), viscosity 10 mPa at 20°C, 2%
solution.
8CMC WALOCEL CRT 5 G (Wolff Walsrode - Germany), viscosity 5 mPa at 20 °C, 2%
solution.
Commercial CMC is a powder soluble in hot water, with constant gentle mixing, leading to a
slightly viscous solution. As mentionned by Tusseau (2009), a complete dissolution of CMC is
necessary before incorporation in wine. So a 20 - 40 g.L-1 CMC solution was prepared, limiting the
introduction of water to 0.1 Ŕ 0.2 L per hL of wine for wine treatment with 20 mg.L-1 of CMC.
3.2. Studied solutions and wines
3.2.1. Model solution
The model solution studied is the same as the one used to study the effect of polysaccharides and
polyphenols on wine tartaric stabilization (Gerbaud, 1996; Gerbaud et al., 1997): 12% v/v alcohol,
2.42 g.L-1 KHT, 2 g.L-1 K2SO4, pH=3.77. It is equivalent to 1.93 g.L-1 of tartaric acid and 1.39 g.L-1 of
potassium. Rigorously computed with the help of MEXTAR® (Blouin et al., 1998; Devatine et al.,
2002; Gerbaud et al., 2003), its saturation temperature equals Tsat=27°C and the crystallisation risk at
11.5°C is evaluated by the supersaturation equal to S=1.67.
3.2.2. Wines
Twenty-one wines were studied:
20 wines during the refrigeration tests:
o From Bordeaux area: 9 dry white wines, 2 sweet wines, 10 red wines
o From Côtes du Rhône AOC: 1 white wine and 1 red wine
o From Nantes area: 2 white wines
1 red wine, noted VR4, during the induction time tests.
All wines were unstabilized (no filtration, no fining). Table 1 displays the chemical analysis of the
wines. Knowledge of pH, total acidity, tartaric acid (TarAc), malic acid (MalAc), and potassium
concentrations enables to assess KHT crystallization risk (supersaturation, saturation temperature and
maximum KHT crystal amount (excess amount) recoverable at -4°C by using MEXTAR® software).
Knowledge of malic and lactic (Lac) acids is not mandatory but improves the accuracy of the
prediction (Blouin et al., 1998).
Table 1 shows that 10 wines (1 white and 9 reds) are supersaturated at 20°C (S>1; Tsat>20°C) and
that all wines are supersaturated at -4°C (1.69The combination of many factors, such as ion distribution, pH, % v/v, etc. is responsible for the
distribution of the supersaturation S values for the wines displayed in table 1.
10Wine Total Free SO2 KHT excess amount
Type Origin Alcohol pH K+ TarAc MalAc LacAc Supersaturation (S) * Tsat
n° Acidity SO2 Total at -4°C **
% v/v g.L-1 mg.L-1 mg.L-1 mg.L-1 g.L-1 g.L-1 g.L-1 at 20°C at -4°C °C g.L-1
1 899 Dry white Muscadet 11.6 4.3 3.23 8 38 700 2.3 3.9 0.18 0.92 2.20 18.0 1.72
2 900 Sweet white Bordeaux 1 13.3 3.9 3.49 76 296 1350 0.8 3.0 0.31 0.80 1.81 14.2 0.77
3 901 Dry white Gros Plant 10.5 5.7 2.97 12 38 400 4.7 4.5 0.15 0.70 1.69 10.0 1.03
4 902 Dry white C. du Rhône 1 12.3 4.7 3.26 12 119 950 3.0 4.0 0.19 1.23 2.92 25.6 2.74
5 903 Sweet white Bordeaux 2 11.5 4.5 3.18 29 178 800 1.9 3.6 0.16 0.87 2.06 16.1 1.57
6 904 Dry white Bordeaux 3 11.4 5.0 3.24 15 63 750 2.3 5.0 0.14 0.93 2.24 18.1 1.78
7 905 Dry white Bordeaux 4 11.3 4.4 3.23 27 135 850 2.0 4.1 0.28 0.94 2.28 18.5 1.74
8 906 Dry white Bordeaux 5 12.0 6.0 3.03 9 58 600 4.3 4.8 0.19 0.83 1.94 14.8 1.41
9 907 Dry white Bordeaux 6 12.1 4.8 3.23 15 113 750 2.4 4.8 0.18 0.95 2.23 18.7 1.79
10 908 Dry white Bordeaux 7 11.6 5.1 3.09 15 70 600 3.0 4.7 0.19 0.87 2.07 16.3 1.61
11 909 Dry white Blayais 1 11.6 4.4 3.31 10 123 950 1.8 4.2 0.57 0.97 2.32 19.4 1.68
12 954 Red Bordeaux 8 12.5 3.1 3.67 15 39 1400 1.6 0.1 2.13 1.15 2.73 23.6 1.71
13 955 Red Medoc 1 12.1 3.2 3.63 19 64 1300 2.0 0.1 2.15 1.23 2.95 25.6 2.16
14 956 Red Bordeaux 9 11.3 3.7 3.64 34 110 1250 1.5 0.0 2.40 1.03 2.52 20.7 1.55
15 957 Red Bordeaux 10 12.1 3.1 3.61 20 62 1200 1.9 0.1 2.16 1.17 2.78 24.0 2.01
16 958 Red Medoc 2 12.4 3.2 3.67 39 91 1350 1.8 0.1 2.04 1.20 2.86 24.7 1.94
17 959 Red Bordeaux 11 11.7 3.4 3.63 20 107 1400 1.7 0.6 2.24 1.15 2.79 23.8 1.88
18 960 Red Blayais 2 11.9 3.1 3.63 26 80 1300 1.4 0.1 2.06 1.03 2.48 20.7 1.5
19 961 Red C. du Rhône 2 12.0 3.2 3.71 18 68 1400 1.5 0.0 2.46 1.10 2.65 22.4 1.59
20 962 Red Bordeaux 12 12.0 4.3 3.60 30 121 1350 1.2 0.2 2.03 0.97 2.32 19.5 1.21
21 VR4 Red Bordeaux 1990 12.9 2.9 3.63 22 57 1014 1.6 0.3 2.00 1.04 2.47 20.8 1.56
-1
+1.5 g.L
VR4
KHT
12.9 3.3 3.61 22 57 1325 2.8 0.3 2.00 1.51 3.50 30.5 3.06
Ac: acid; Mal: malic; Tar: tartaric; Lac: lactic * S, Tsat computed with MEXTAR. ** computed with MEXTAR to reach saturation at -4°C
Table 1: Chemical analysis of wines
114. Inhibition ratio measurement in model solutions and in a red
wine
The induction time was recorded in 150 mL of solution, either model solution or wine VR4, under
continuous magnetic stirring and constant temperature, with and without additive in order to compute
the inhibition ratio.
Without additive at 11.5°C (S=1.67), the induction time of the model solution equals 1 hr 20 min
15min, averaged over 38 measurements. Such a model solution has no protective colloids and the
KHT crystallization is much faster than in a red wine at the same supersaturation (Gerbaud, 1996).
Without additive, wine VR4 + 1.5 g.L1 of KHT shows a mean induction time equal to 1 hr 15 min
at 11.5°C (S=2.02).
4.1. Effect of CMC in a model solution
The inhibition ratio values for the model solution are presented in table 2 (S=1.67; T=11.5°C) and
table 3 (S=2.38; T=2°C).
Model solution Cadditive (mg.L-1) 0.5 1 2 6 10
CMC Inhibition ratio 1.56 1.70 2.23 > 45
Blanose7LF Crystal occurrence* + + + 0
CMC Walocel Inhibition ratio > 28
CRT 5G Crystal occurrence* 0
CMC Walocel Inhibition ratio > 37
CRT 10G Crystal occurrence* 0
* +: crystal appearance; 0: experience stopped before crystal appearance.
Table 2. Inhibition ratio in a model solution 12% v/v (S=1.67; T=11.5°C)
Model solution Cadditive (mg.L-1) 8 30
CMC Inhibition ratio 1.15 23.32
Blanose7LF Crystal occurrence* + +
* +: crystal appearance.
Table 3. Inhibition ratio in a model solution 12% v/v (S=2.38; T=2°C)
All three CMCs exhibit an inhibitory effect that increases with increasing CMC concentration,
starting at concentration as low as 0.5 mg.L-1 (0.05 g.hL-1)! Compared to results obtained for
polyphenols and polysaccharides on the same model solution under the same conditions (see section
122.3), CMC is a much better inhibitor, reaching equivalent or higher inhibition ratio at concentrations
10 times lower than polysaccharides and 50 to 200 times lower than polyphenols.
When the crystallization risk is increased through the supersaturation by decreasing the
temperature to 2°C, CMC still has a strong inhibitory effect, but concentrations 3 to 5 times higher
than at 11.5°C are needed to reach the same inhibition ratio.
4.2. Effect of CMC in a highly unstable wine at 11.5°C
Addition of 1.5 g.L-1 of KHT to wine VR4 is equivalent to a wine with 1.3 g.L-1 of potassium and
2.8 g.L-1 of tartaric acid. The resulting wine is the most unstable of all wines studied, with a saturation
temperature equal to 30.5°C (table 1).
Inhibition ratios at 11.5°C (S= 2.02) are presented in table 4.
Wine Cadditive (mg.L-1) 2.5 10
VR4 + 1.5 g.L-1 KHT
CMC Inhibition ratio > 40 > 65
Blanose7LF Crystal occurrence* 0 0
* 0: experience stopped before crystal appearance.
Table 4. Inhibition ratio of wine VR4 added with 1.5 g.L-1 of KHT (S=2.02; T=11.5°C)
Again, CMC displays a strong inhibitory effect at 2.5 mg.L-1, increasing in parallel with increasing
CMC concentrations. The effect is seemingly stronger than in model solutions, likely due to the
protective effect of natural polyphenols and polysaccharides already mentionned.
Moreover, wine VR4 has also 0.1 g.L-1 of calcium. With the addition of 1.5 g.L-1 of KHT,
MEXTAR® software predicts that the resulting wine is undersaturated for calcium tartrate at 20°C
(SCaT=0.94) and slightly supersaturated at 11.5°C (SCaT=1.21). However, no calcium salt precipitates
were detected. It is acknowledged that CaT precipitates after KHT, and that KHT precipitation
decreases the calcium salt crystallization risk (Ratsimba, 1990).
5. Effect of CMC in wine after refrigeration test
Recording of the presence or absence of crystals after refrigeration for 3 weeks at -4°C was
performed in the cellar of the Gironde Chamber of Agriculture in Blanquefort, on 20 wines described
in table 1. For each experimental condition, results are the average of three bottles.
5.1. Refrigeration test
Following the same procedure than above, wines treated with either CMC or metatartaric acid
were kept at -4°C for 3 weeks and crystal occurrence was checked. Table 5 presents the results and
recalls the supersaturation values computed with MEXTAR®.
13Tartaric acid and potassium analyses done on blank samples (without additives) that displayed
crystals showed no significative differences among the wines, because the crystal amount
corresponded to concentration differences that were less than the common chemical analysis standard
deviation (according to OIV/EEC regulations).
+ 5 mg.L-1 + 20 mg.L-1
Supersaturation + 100 mg.L-1
Blank CMC CMC
Wine Wine Metatartaric
sample BLANOSE BLANOSE
n° (W)hite or (R)ed acid
at 20°C at -4°C 7LF 7LF
-4°C during 3 weeks
899 Muscadet (W) 0.92 2.20 ++ 0 0 0
900 Cadillac (W) 0.80 1.81 ++++ 0 0 0
901 Gros plant (W) 0.70 1.69 ++ 0 0 0
902 Côtes du Rhône (W) 1.23 2.92 ++++ 0 0 0
903 Soussac 1 (W) 0.87 2.06 + 0 0 0
904 Soussac 2 (W) 0.93 2.24 ++ 0 0 0
905 Grezillac (W) 0.94 2.28 + 0 0 0
906 600 n°9 (W) 0.83 1.94 ++++ 0 0 0
907 604 Sauvignon (W) 0.95 2.23 +++ 0 0 0
908 604 Muscadelle (W) 0.87 2.07 ++ 0 0 0
909 Blaye (W) 0.97 2.32 ++ 0 0 0
954 Coutras (R) 1.15 2.73 ++ 0 0 0
955 Pauillac Ht Medoc (R) 1.23 2.95 +++ 0 0 0
956 604 CS temoin (R) 1.03 2.52 +++ 0 0 0
957 Grezillac temoin (R) 1.17 2.78 +++ 0 0 0
958 Pauillac (R) 1.20 2.86 +++ 0 0 0
959 Cadillac temoin (R) 1.15 2.79 +++ 0 0 0
960 Blaye temoin (R) 1.03 2.48 +++ 0 0 0
961 Côtes du Rhône (R) 1.10 2.65 ++ 0 0 0
962 604 CF temoin (R) 0.97 2.32 + 0 0 0
Crystal amount: 0 none; + to ++++ increasing amount
Table 5. Tartaric stabilization of wine by addition of CMC Blanose 7LF or metatartaric acid
after refrigeration at -4°C for 3 weeks
Table 5 shows that all blank samples exhibit various crystal amounts (recorded visually). In spite
of the qualitative feature of a visual observation, the crystal amount seems correlated with
supersaturation for red wines, but not for white wines.
14None of the wines treated with additives, 5 or 20 mg.L-1 CMC or 100 mg.L-1 metatartaric acid,
show crystals. We conclude that after 3 weeks of cooling at -4°C, 5 mg.L-1 CMC has the same
inhibitory efficiency as 100 mg.L-1 metatartaric acid.
5.2. Heating followed by refrigeration test
5.2.1. Model solution tests
In order to evaluate the stability of CMC under heating, a clear drawback of metatartaric acid, the
model solution was added with 20 mg.L-1 CMC or with 100 mg.L-1 metatartaric acid, heated for 2 hrs
at 40°C, then cooled at 11°C and agitated for 100 hrs.
Table 6 shows that the metatartaric acid efficiency is destroyed by heating which induces
hydrolysis of tartaric acid, thus reinforcing the wine unstability.
Model solution Cadditive (mg.L-1) Heating Cooling Crystals
20 Ambient 0
CMC Blanose7LF 11°C, 100 hrs
temperature
CMC Blanose7LF 20 2 hrs at 40°C 11°C, 100 hrs 0
100 Ambient 0
Metatartaric acid 11°C, 100 hrs
temperature
Metatartaric acid 100 2 hrs at 40°C 11°C, 100 hrs ++++
Table 6. Heating impact on metatartaric acid and CMC BLANOSE 7LF effect on tartaric
precipitation in model solution
5.2.2. Wine tests
Ten wines were kept at 30°C for 8 days, then refrigerated at 0°C for 2 months. Results are reported
in table 7.
+ 5 mg.L-1 + 20 mg.L-1 + 100 mg.L-1
CMC CMC metatartaric
Wine Wine BLANOSE 7LF BLANOSE 7LF acid
n° (W)hite or (R)ed
+ 8 days at 30°C followed by 2 months at 0°C
900 Cadillac (W) 0 0 0
901 Gros plant (W) + 0 ++
902 Côtes du Rhône (W) 0 0 (+)
15906 600 n°9 (W) 0 0 0
907 604 Sauvignon (W) + (+) ++
954 Coutras (R) ++ N.A. +
958 Pauillac (R) +? +? 0
959 Cadillac temoin (R) 0 0 0
960 Blaye temoin (R) +? +? 0
961 Côtes du Rhône (R) 0 0 0
Crystal amount: 0 none; + to ++++ increasing amount
(+) suspected. +?: peculiar star-like crystals.
Table 7. Heat impact on metatartaric acid and CMC BLANOSE 7LF effect on tartaric
precipitation in wines
Again, the results show that 100 mg.L-1 metatartaric acid looses its inhibitory efficiency as 4 cases
out of 10 exhibit crystals. At 5 mg.L-1, CMC does not prevent the presence of crystals in 5 cases out
of 10, including 2 cases with atypical star-like crystals. At 20 mg.L-1 CMC, only 1 case exhibits KHT
crystal deposit and the same 2 "+?" cases as with 5 mg.L-1 exhibit atypical star-like crystals.
The star-like crystals are distinct from the usual rhomboedral shape of KHT crystals (Rodriguez-
Clemente and Correa-Gorospe, 1988; Gerbaud, 1996). They could well be crystals of another
chemical substance but that was not further investigated during the tests. Gerbaud (1996) and
Crachereau et al. (2001) investigated the effect of CMC on KHT crystal shapes and noted that CMC
flattened the crystals and slowed the growth by a factor 7. More specifically, CMC slowed the growth
of the main crystallographic face (010), hinting at a strong interaction between this face, that displays
overall electropositive charges due to potassium ions, and CMC that is negatively charged under wine
pH conditions. Thus, CMC competes with K+ and HT- ions in solution, preventing their attachement
to the crystal faces (figure 1). The (130) and (101) crystallographic faces also disappear with CMC,
because their relative growth rate becomes too large compared to the growth of the (010) face.
16KHT crystals without CMC KHT crystals with CMC
Face altered by CMC
Face disappeared
Figure 1. Sketch of potassium hydrogen tartrate crystals with and without CMC.
Haziness was observed in some wines, that corresponds to non crystalline precipitations usually
observed in unstabilized (filtration, fining) wines, such as those used, that are kept under low
temperature for long periods.
6. Discussion
The results are in agreement with those reported by Wucherpfennig et al. (1984), Crachereau et al.
(2001) and Motta et al. (2009). They evidence the inhibitory effect of CMC at very low
concentrations, several times lower that those of other inhibitors like protective colloids and
metatartaric acid, in a model solution and in a selection of wines.
More specifically, 20 mg.L-1 CMC has an inhibitory effect equivalent to 100 mg.L-1 metatartaric
acid, also withstanding heating, which is not the case of metatartaric acid. CMC is not a complete
inhibitor but its efficiency increases with concentration, without showing any limiting efficiency.
7. Conclusion
Recording the induction time by monitoring the conductivity in a model solution and in a wine has
enabled to compute the inhibition ratio and to compare the inhibitory effect of CMC on tartaric acid
salt precipitation with that of natural protective colloids present in wines, like polyphenols and
polysaccharides.
Results show that CMC has a better inhibitory effect than polysaccharides at 10 times lower
concentration and an equivalent inhibitory effect to that of polyphenols at 50 to 200 times lower
concentration at 11.5°C. Furthermore, the inhibitory effect is maintained at 2°C, when the
crystallisation risk is increased. In that case, 3 to 5 times greater concentration are needed to achieve
the same effect than at 11.5°C.
17Refrigeration tests were performed on wines to record the presence or absence of crystals. Results
from the experimental conditions (3 weeks at -4°C for 20 white and red wines; or 8 days at 30°C
followed by 2 months at 0°C) show that 20 mg.L-1 CMC has an inhibitory effect on potassium
hydrogen tartrate crystallization equivalent to 100 mg.L-1 metatartaric acid. Besides, the CMC
efficiency increases in parallel with increasing CMC concentration, without showing any limiting
efficiency.
The same observation is made for 10 wines heated for 8 days at 30°C and then refrigerated for 2
months at 0°C. This severe treatment reduces the metatartaric efficiency by 40%. For 5 mg.L-1 CMC,
30% of the wines have tartaric crystals and 20% have other unidentified crystals. For 20 mg.L-1 CMC,
10% of the wines have tartaric crystals and the same other 20% have again unidentified crystalline
haziness.
The efficiency of 20 mg.L-1 low molecular weight CMC that match the OIV-OENO 366-2009 and
OIV-OENO 02/2008 resolution is confirmed to prevent tartaric acid salt precipitation, in agreement
with other studies on the topic. With no impact on health, stable under heating and in acid solution,
without viscosity effect at the very low concentration considered (Crachereau et al., 2001), CMC is a
new candidate for tartaric stabilization when its full dissolution before incorporation is achieved.
However, the 20 mg.L-1 (2 g.hL-1) dose should be reconsidered for practical application with the help
of winemakers, depending on the local context of the wine supersaturation and storage
Acknowledgments
The authors want to thank the Gironde Chamber of Agriculture for its support and fruitful
discussions with D. Bunner and D. Tusseau at the Champagne Wine Comitee CIVC. Besides
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